Branched surfactant manufacture

ABSTRACT

Alpha-olefins are dimerized to form branched-chain feedstocks for detersive surfactants.

CROSS REFERENCE

This is a continuation of PCT International application Serial No.PCT/US97/06485, filed Apr. 16, 1997; which claim priority to ProvisionalApplication Ser. No. 60/015,521, filed Apr. 16, 1996.

FIELD OF THE INVENTION

The present invention relates to processes for manufacturing detersivesurfactants, especially those containing branched-chain hydrophobicunits.

BACKGROUND OF THE INVENTION

Conventional detersive surfactants comprise molecules having awater-solubilizing substituent (hydrophilic group) and an oleophilicsubstituent (hydrophobic group). Such surfactants typically comprisehydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide,polyoxyethylene, and the like, attached to an alkyl, alkenyl or alkarylhydrophobe usually containing from about 10 to about 20 carbon atoms.Accordingly, the manufacturer of such surfactants must have access to asource of hydrophobe groups to which the desired hydrophile can beattached by chemical means. The earliest source of hydrophobe groupscomprised the natural fats and oils, which were converted into soaps(i.e., carboxylate hydrophile) by saponification with base. Coconut oiland palm oil are still used to manufacture soap, as well as tomanufacture the alkyl sulfate (“AS”) class of surfactants. Otherhydrophobes are available from petrochemicals, including alkylatedbenzene which is used to manufacture alkyl benzene sulfonate surfactants(“LAS”).

The literature asserts that certain branched hydrophobes can be used toadvantage in the manufacture of alkyl sulfate detersive surfactants;see, for example, U.S. Pat. No. 3,480,556 to deWitt, et al., Nov. 25,1969. However, it has been determined that the beta-branched surfactantsdescribed in the '556 patent are inferior with respect to certainsolubility parameters, as evidenced by their Krafft temperatures. It hasfurther been determined that surfactants having branching towards thecenter of carbon chain of the hydrophobe have much lower Kraffttemperatures. See: “The Aqueous Phase Behavior of Surfactants”, R. G.Laughlin, Academic Press, New York (1994) p. 347. Accordingly, it hasnow been determined that such surfactants are preferred for useespecially under cool or cold water washing conditions (e.g., 20° C.-5°C.).

One problem associated with the manufacture of detersive surfactantshaving hydrophobe groups with mid- or near-mid chain branching is thelack of a ready source of such hydrophobes. By the present invention, aprocess is described for manufacturing such branched hydrophobes andconverting them into mid- or near-mid chain branched surfactants.

SUMMARY OF THE INVENTION

The present invention encompasses a process for preparing mid- to nearmid-chain branched olefins (primarily, methyl branched at or near themid-chain region). Such materials are then used as the basic feedstockwhich provides the hydrophobic portion of branched-chain detersivesurfactants.

The process herein is illustrated by the following reaction sequence.

1) Alpha-Olefin Dimerization

 wherein R and R′ may be the same or different linear alkyl, and whereinR is C₃-C₇, preferably C₅ to C₇ linear alkyl, and R′ is C₃-C₇,preferably C₅-C₇ linear alkyl. For use in preparing surfactants incleaning products such as laundry detergents, dishwashing liquids, andthe like, R and R′ are preferably the same or within one or two carbonatoms of each other in chain length. Some linear olefins may also resultfrom the dimerization and these can optionally be removed usingmolecular sieves. Step 1 of the process herein is designed to providebranched olefins which preferably contain from about 12 to about 18(avg.) total carbon atoms.

2) Alcohol Production

In Step 2 (Route A), the olefin mixture for Step 1 can be pre-randomizedto enhance the ultimate formation of alcohols (i) and (ii) in subsequentStep 3. Alternatively (Step 2, Route B), this pre-randomization step canbe deleted and the Oxo catalyst, itself, can randomize the final productamong the three possible terminal positions.

The Oxo process to make alcohols is described in detail in Kirk-OthmerEncyclopedia of Chemical Technology, 4th Edition, Volume 1, pp. 903-8(1991), Jacqueline I. Kroschwitz, Executive Editor, Wiley-Interscience,New York. The catalyst for this step is, for example, cobalt-carbonmonoxide-organophosphine.

The alcohol mixture of Step (2) of the present process comprisesbranched-chain primary alcohol compounds of the following formulae foruse in Step (3), below.

It is to be understood that when CH₂OH is substituted on R or R′ it isprimarily on their respective terminal carbons or to a lesser extent ontheir penultimate carbons. Desirably, minimal amounts of compounds ofthe formula (iii) are present in Step (3).

3) Surfactant Production

Advantageously, the present process results in no geminal branching,i.e., no “quaternary” carbon substitution. Steric hindrance will blockinverse addition to vinylidene carbon with cobalt-carbonmonoxide-organophosphine which otherwise would form a non-biodegradablequaternary carbon. Moreover, little (less than about 3%) vicinalbranching occurs. Of course, some of the overall feedstock may remainunbranched. Typically, and preferably from the standpoint of cleaningperformance and biodegradability, the present process provideshydrophobes with one near-central methyl in the case of isomers i) andii).

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All documents cited herein are, in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

1) Olefin Dimerization

The present invention encompasses, in a process for preparing surfactantprecursor hydrophobes from dimerization of two same or near same chainlength alpha-olefins to form a detergent range vinylidene olefin. Thesealpha olefins C₅ to C₁₀, preferably C₇ to C₉ are dimerized to give C₁₀to C₂₀, preferably C₁₄ to C₁₈ vinylidene olefins which upon Oxo reactiongive C₁₁ to C₂₁, preferably C₁₅ to C₁₉ alcohols. There are a number ofprocesses for accomplishing said dimerization; see U.S. application Ser.No. 9,200,398, U.S. Pat. Nos. 4,658,078, 4,973,788; O. S. Vostrikova, A.G. Ibragimov, G. A. Tolstikov, L. M. Zelenova and U. M. Dzhemilev, Izv.Akad. Nauk SSSR, Ser. Khim. (1980), (10), 2330-2 [Chem. Abstr.94:65032]; Jpn. Kokai Tokkyo Koho, 06228016 A2 [Chem. Abstr.122:186930].

2) Alcohol Production

Route A

Part a)

The carbon-carbon double bond of the vinylidene olefin is pre-isomerizedusing a method such as Shell uses to isomerize alpha-olefins in theirSHOP process; see Kirk-Othmer Encyclopedia of Chemical Technology, 4thEdition, Volume 17, pp. 848-50 (1996), Jacqueline I. Kroschwitz,Executive Editor, Wiley-Interscience, New York and Chemical EconomicsHandbook, pp. 681.5030K-L, Stanford Research Institute, Menlo Park,Calif. 94025, October 1993.

Part b)

Oxo chemistry is used to convert the pre-isomerized vinylidene olefin(now largely internal olefin) to a primary alcohol mixture. For this anOxo catalyst which isomerizes the double bond to alpha positions priorto carbonylation is desired as is the case usingcobalt-carbonyl-phosphine catalysts in the one step process, seeKirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 1,pp. 903-8 (1991). Route A, (that is including pre-isomerization) isundertaken to assure relatively high yields of alcohols i and ii versusalcohol iii. Note alcohol sulfates of i and ii are desired surfactantswhereas that of iii may be deficient.

Route B

This step utilizes the same Oxo catalyst on the vinylidene olefindirectly without its pre-isomerization. This relies upon the catalyst tocompletely isomerize the carbon-carbon double bond of the vinylideneolefin prior to carbonylation. The object is to obtain as much i and iirelative to iii as is obtained in Route A.

Other fatty alcohol-derived surfactants can also be made, e.g., alkylethoxyl sulfates (AES), alkyl polyglucosides (APG), etc. Note thatsurfactants other than alcohol sulfates or AES may be made by oxidizingsaid alcohol or its aldehyde intermediate into a carboxylate (i.e., abranched-chain soap). This soap can be an excellent surfactant and/ordetergent builder in and of itself. This carboxylate can also be used asa feedstock and converted to branched acyl-taurates, -isethionates,-sarcosinates, -N-methylglucamide or other acyl-derived surfactantsusing art-disclosed techniques.

INDUSTRIAL APPLICABILITY

Branched-chain surfactants of the type resulting from the presentprocess can be used in all manner of cleaning compositions. Suchcompositions include, but are not limited to: granular, bar-form andliquid laundry detergents; liquid hand dishwashing compositions; liquid,gel and bar-form personal cleansing products; shampoos; dentifrices;hard surface cleaners, and the like. Such compositions can contain avariety of conventional detersive ingredients. The following listing ofsuch ingredients is for the convenience of the formulator, and not byway of limitation of the types of ingredients which can be used with thebranched-chain surfactants herein.

The branched-chain surfactants herein can be used in combination withdetergency builders. Such builders include, for example, 1-10 micrometerzeolite A, polycarboxylate builders such as citrate, layered silicatebuilders such as “SKS-6” (Hoechst) and phosphate materials, especiallysodium tripolyphosphate (“STPP”). Most laundry detergents typicallycomprise at least about 1% builder, more typically from about 5% toabout 80% builder or mixtures of builders.

Enzymes, such as proteases, amylases, lipases, cellulases, peroxidases,and mixtures thereof, can be employed in detergent compositionscontaining the branched-chain surfactants. Typical detergentcompositions comprise from about 0.001% to about 5% of commercialenzymes.

Detergent compositions can also contain polymeric soil release agents(SRA's). Such materials include, for example, anionic, cationic andnon-charged monomer units, especially polyester materials. Preferredmaterials of this type include oligomeric terephthalate esters,sulfonated substantially linear ester oligomers comprising a backbone ofterephthaloyl and oxyalkyleneoxy repeat units and phthalolyl-derivedsulfonated terminal moieties. A variety of SRA's are described, forexample, in U.S. Pat. Nos. 4,968,451; 4,711,730; 4,721,580; 4,702,857;4,877,896; 5,415,807; and in other literature references. Such soilrelease materials typically comprise from about 0.01% to about 10% offinished detergent compositions.

Detergent compositions may also optionally contain bleachingcompositions comprising a bleaching agent and one or more bleachactivators. If present, bleaching agents such as percarbonate orperborate (especially perborate monohydrate “PB1”) typically are used atlevels from about 1% to about 30% of finished detergent compositions.Bleach activators such as nonanoyloxy-benzene sulfonate (“NOBS”) andtetraacetyl ethylenediamine (“TAED”), and mixtures thereof, can be usedto enhance the bleaching activity of materials such as perborate andpercarbonate. If present, the amount of bleach activator will typicallybe from about 0.1% to about 60% of a bleaching composition comprising ableaching agent-plus-bleach activator. Other bleaching agents such asthe so-called “photoactivated” bleaches (see U.S. Pat. No. 4,033,718)can also be used. Sulfonated zinc phthalocyanine is an especiallypreferred photoactivated bleaching agent.

Detergent compositions can also contain clay soilremoval/antiredeposition agents such as ethoxylated tetraethylenepentamine; see U.S. Pat. No. 4,597,898. Such materials typicallycomprise from about 0.01 to about 10% to about 1001% of fully-formulatedlaundry detergents.

Detergent compositions can also contain from about 0.1% to about 7% ofpolymeric dispersing agents, which are especially useful in the presenceof zeolite and/or layered silicate builders. Such materials are known inthe art (see U.S. Pat. No. 3,308,067). Such materials includeacrylate/malic-based copolymers, such as described in EP 193,360, aswell as polyethylene glycol (“PEG”).

Detergent compositions herein can also include various brighteners, dyetransfer inhibiting agents (especially polymers of N-vinylpyrrolidoneand N-vinylimidazole), suds suppressors (especially silicones),chelating agents such as nitilotiacetate, ethylenediamine disuccinate,and the like. Such materials will typically comprise from about 0.5% toabout 10%, by weight, of fully-formulated cleaning compositions.

Moreover, it is to be understood that the branched-chain surfactantsprepared in the manner of the present invention may be used singly incleaning compositions or in combination with other detersivesurfactants. Typically, fully-formulated cleaning compositions willcontain a mixture of surfactant types in order to obtain broadscalecleaning performance over a variety of soils and stains and under avariety of usage conditions. One advantage of the branched-chainsurfactants herein is their ability to be readily formulated incombination with other known surfactant types. Nonlimiting examples ofadditional surfactants which may be used herein typically at levels fromabout 1% to about 55%, by weight, include the unsaturated sulfates suchas oleyl sulfate, the C₁₀-C₁₈ allyl alkoxy sulfates (“AE_(×)S”;especially EO 1-7 ethoxy sulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates(especially the EO 1-5 ethoxycarboxylates), the C₁₀₋₁₈ glycerol ethers,the C₁₀-C₁₈ alkyl polyglycosides and their corresponding sulfatedpolyglycosides, and C₁₂-C₁₈ alpha-sulfonated fatty acid esters. Nonionicsurfactants such as the ethoxylated C₁₀-C₁₈ alcohols and alkyl phenols,(e.g., C₁₀-C₁₈ EO (1-10) can also be used. If desired, otherconventional surfactants such as the C₁₂-C₁₈ betaines and sulfobetaines(“sultaines”), C₁₀-C₁₈ amine oxides, and the like, can also be includedin the overall compositions. The C₁₀-C₁₈ N-alkyl polyhydroxy fatty acidamides can also be used. Typical examples include the C₁₂-C₁₈N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactantsinclude the N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈glucamides can be used for low sudsing. C₁₀-C₂₀ conventional soaps mayalso be used. If high sudsing is desired, the branched-chain C₁₀-C₁₆soaps may be used. C₁₀C₁₄ alkyl benzene sulfonates (LAS), which areoften used in laundry detergent compositions, can also be used with thebranched surfactants herein.

The following Examples illustrate the use of branched-chain surfactantsprepared according to the present invention in various cleaningcompositions, but is not intended to be limiting thereof.

EXAMPLE I

Granular laundry detergents are prepared as follows.

A B C Blown Powder Zeolite A 30.0 22.0 6.0 Sodium sulfate 19.0 5.0 7.0Polyacrylate LAS 13.0 11.0 21.0 Branched AS* 9.0 8.0 8.0 Silicate, Na —1.0 5.0 Soap — — 2.0 Carbonate, Na 8.0 16.0 20.0 Spray On C₁₄₋₁₅EO7 1.01.0 1.0 Dry additives Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS — 6.1 4.5 PB1 1.0 5.0 6.0 Sodiumsulfate — 6.0 — Moisture & Miscellaneous--------------Balance------------- *C₁₂—C₁₄ methyl branched alkylsulfate, prepared as disclosed above.

A bleach-containing nonaqueous liquid laundry detergent is prepared asfollows.

EXAMPLE II

Component Wt. % Range (% wt.) Liquid Phase Branched AS* 25.3 18-35C₁₂₋₁₄, EO5 alcohol ethoxylate 13.6 10-20 Hexylene glycol 27.3 20-30Perfume 0.4  0-1.0 Solids Protease enzyme 0.4  0-1.0 Na₃ Citrate,anhydrous 4.3  3-6 Sodium perborate (PB-1) 3.4  2-7 Sodiumnonanoyloxybenzene sulfonate 8.0  2-12 (NOBS) Sodium carbonate 13.9 5-20 Diethyl triamine pentaacetic acid (DTPA) 0.9  0-1.5 Brightener 0.4 0-0.6 Suds Suppressor 0.1  0-0.3 Minors -----Balance----- *C₁₂—C₁₆methyl branched alkyl sulfate, Na salt, prepared as disclosed above.

A hand dishwashing liquid is as follows.

Ingredient % (wt.) Range (% wt.) Branched AS* 13.0  5-15 Ammonium C₁₂₋₁₃alkyl 15.0 10-35 ethoxy sulfate Coconut amine oxide 2.6  2-5Betaine**/Tetronic 704 ® 0.87-0.10  0-2 (mix) Alcohol Ethoxylate C₈E₁₁5.0  2-10 Ammonium xylene sulfonate 4.0  1-6 Ethanol 4.0  0-7 Ammoniumcitrate 0.06  0-1.0 Magnesium chloride 3.3  0-4.0 Calcium chloride 2.5 0-4.0 Ammonium sulfate 0.08  0-4.0 Hydrogen peroxide 200 ppm  0-300 ppmPerfume 0.18  0-0.5 Maxatase ® protease 0.50  0-1.0 Water and minors--------------Balance----------- *C₁₂C₁₄ methyl branched alkyl sulfate,triethanolammonium salt, prepared as disclosed above. **Cocoalkylbetaine.

What is claimed is:
 1. A process for preparing branched alkylcarboxylate surfactants, comprising the steps of: (a) dimerizing alphaolefins of the formula RCH═CH₂ and R′CH₂═CH₂, to form olefins of theformula:

 wherein in the above formulas R and R′ may be the same or different C₃to C₇ linear alkyl substituents; followed by either (b) isomerizing theolefins from Step (a) and the subsequent reaction of said isomerizedolefins with CO/H₂ under Oxo conditions using acobalt-carbonyl-phosphine catalyst; or directly reacting the olefinsfrom Step (a) with CO/H₂ under Oxo conditions using acobalt-carbonyl-phosphine catalyst; and (c) recovering branched alcoholsof the formula:

(d) oxidizing the alcohols or their aldehyde intermediates recoveredfrom Step (c); and, (e) recovering the desired branched alkylcarboxylate surfactants.
 2. A process for preparing branched acyltaurate, branched acyl isethionates, branched acyl sarcosinates, orbranched acyl N-methylglucamine surfactants using the branched alkylcarboxylate surfactants prepared according to claim 1 as a feedstock.